Process for manufacture of glycidyl ethers of polyhydric phenols



P. PEZAGLIA PROCESS FOR MANUFACTURE OF GLYCIDYL June 24, 1958 ETI-1BRS oF POLYHYDRIC PHENoLs Filed Jan. 31, 1955 ...03m-ONE s C EEE 5.5.; m om INVENTOR PHILIP PEZZAGLIA BY m/f HIS ATTORNEY United States Patent C) PROCESS FOR MANUFACTURE oF GLYCIDYL ETHERs or PoLYHYDRIc rHENoLs Philip Pezzaglia, El Cerrito, Calif., assignor toShell Development Company, New York, N. Y., a corporation of Delaware Application January 31, 1955, Serial No. 484,869v

Claims. (Cl. 260-47) wherein n is an integer of theseries O, l, 2, 3, etc., and R represents the divalent radical to which the two phenolic hydroxyl groups are attached in the dihydric phenol.

VIt is desirable that the glycidyl ether product contain as much as possible of the compound wherein n is zero, i. e., the diglyci-dyl diether of the dihydric phenol. It was discovered'heretofore that by having presenta substantial excess of epichlorohydrin lin the reactionfmixture over the stoichiometric proportion of 2 moles of; epichlorohydrin per mole of the phenol, and'adding an equivalent of sodium hydroxide perequivalent of epichlorohydrin that combines with vthe dihydric phenol in a batch process, the formation of compoundsin the product having n greaterV than zero is suppressed. rWhile the use Yof such a batch method is of value for increasingthe yeld of the desired glycidyl ether, reasons n of eflcientrcommercial scale manufacture of the epoxy resins necessitate that productionV of the resin be conducted in acontinuous manner.

Upon adapting the aforementioned method to continuous production of the epoxy resin withcontinuousv feeding in of excess epichlorohydrin and dihydric phenol, regulated continuousaddition of sodium hydroxide and continuous withdrawal of product from a reaction zone, I learned that the' formation oftheless desired higher compounds in the product was unfortunately over four times greater than when the methodwas'conducted in an otherwisel parallel batchwise manner. I then discovered that by effecting the preparation in continuous fashion using a series of stages with addition of the caustic in portions to the several stages, the formation of the higher products was reduced effectively. A

According to the process of the invention, a polyhydric phenol and sufficient epichlorohydrin to amountvto at least'two molecules thereof per phenolic hydroxyl group of the phenol are'introduced continuously to the iirst' of a series of successive reaction zones. Reaction mixture is continuously transferred from zone to zone in the yseries (including continuous withdrawal of reaction mixture f romthe lastzone), and alkali metal hydroxide is continuously` introduced to the several zones in fractionsl with the total thereof amounting to about an equivalent of the hydroxide Vper equivalent of the epichlorohydrin that reacts in the whole of the series of zones. The liquid reaction mixture in the several zones is agitated and prefera bly boiled while distilling water therefrom azeotropically with epichlorohydrin so that the water concentration in the reaction mixture is maintained from about 0.2 to 4% by weight. The rates of introduction of reactants, transfer of reaction mixtures and withdrawal of product are regulated so that the liquid contents in the several zones are maintained substantially constant. The improved process is illustrated in the attached drawing.

As shown in the ow diagram of the drawing wherein continuous production of glycidyl ether from a dihydric phenol (diphenol) is illustrated, the improved process of the invention in one embodiment involves use of two rcaction stages. A mixture or solution of diphenol in epichlorohydrin is fed from container 10 by pump 11 through valve 12 into reactor 13 tted with an agitator or stirrer, and means for heating its contents. It is convenient to introduce the epichlorohydrin and diphenol into the reactor as the solution containing the desired ratio of reactants. The epichlorohydrin is used in a ratio of at least 2 molecules of epichlorohydrin per phenolic hydroxyl group of the phenol, i. e., at least 2 moles of epichlorohydrin per phenolic hydroxyl equivalent of the phenol. The feed to reactor 13 as the solution of polyhydric phenol in epichlorohydrin may thus contain 2, 3, 5, 10 or more moles of epichlorohydrin per phenolic hydroxyl equivalent of the phenol. If desired, the epichlorohydrin and phenol may be fed separately to the reactor, or a solution of the phenol in part of the epichlorohydrin and the remaining chlorohydrin may be separately introduced into the reactor.

Aqueous caustic asthe alkali metal hydroxide reactant is introduced from container 14 by pump 15 through valve 16 into reactor 13. Only part of the needed equivav lent of hydroxide per equivalent of epichlorohydrinthat combines with the phenol in the process as a whole is introduced into the rst reactor. When there are two reactors providing two reaction zones as shown in the drawing, it is desirable that about 40 to 75% of the needed hydroxidef'be introduced into the irst reaction zone. Excellent results are obtained with two reactors when about 65% of the caustic is used in theA rst zone and the remainder in the second. However, the hydroxide may be apportioned as desired among two or more zones with good effect. Although not essential, it is convenient to add the alkali metal hydroxide, such as sodium or potassium hydroxide, as an aqueous solution which contains at least about 15% by weight up to the saturation concentration of the hydroxide. It is preferred to use a solution containing about 40% of the hydroxide. Ordinary 48 B. commercial caustic soda is also suitable. The total amount of alkali metal hydroxide used in the process is an equivalent of the hydroxide per equivalent of the epichlorohydrin reacted. This amount of hydroxide Ais ordinarily somewhat less than the phenolic lhydroxyl equivalents ofthe phenol fed to the reactionI sys tem. This is Vbecause the higher ether products require less ythan this equivalent amount of hydroxide. For example, if the product' in using a dihydric phenol were exclusively the simple diether so that n would be equal to zero in the formula given hereinbefore, then 2 moles of epichlorohydrin per mole of the phenol would have re-y acted and 2 moles of the hydroxide would be required. However, some higher ether with n equal to l also forms. This ether resnlts'from reaction of 3 moles of epichlorohydrin'with 2 Ymoles of the phenol so only 1.5 moles of epichlorohydrin havereacted per mole of the phenol, and

, consequently, only .-1.5 moles of the hydroxide is required.v

Patented June 24, s-

Thus when the product consists 4of say 80 mole percent of the diether (n=) and 20mole percent of the triether (n=1), then the hydroxide required would bel moles` per Jmole of the phenol since this is the number of equivalents of epichlorohydrin that has reacted. If the ether product containsl some .organically bound chlorine `due to incomplete. .dehydrochlorinatiom somewhat less than the equivalent amount `of hydroxide is needed. However, some by-products of epichlorohydrin such as glycidol, glycerol, etc., will consume hydroxide in their formationwith` the result that somewhat more than the equivalent amount of hydroxide is required.` These opposing requirements tend in general to balance one another.` The important point is that suicient hydroxide asa whole should be used that :the ether product leaving the last reaction zone is substantially free of organically bound `chlorine and that the reaction mixture is substantially neutral.

In reactor 13, the reaction `mixture 17 is agitated and heated at boiling temperature. Most of the water introduced'with the aqueous caustic and `water of reaction are distilledl from` the reaction mixture azeotropically with epichlorohydrin, the vapor passing to condenser 18 and the condensed distillate to separator 19 where` it separates intoan upper water layer and a lower epichlorohydrin layer.` The rate of distillation which removes water is regulated so that the reaction mixture contains about 0.2 to 4%' by weight, preferably about 0.5 to 2% by weight, of water.

The distilled vapor passing to condenser 18 is not necessarilywthe equilibrium azeotrope of epichlorohydrin and water `since the boilingreaction mixture is too deficient in'` water.' Nevertheless,` upon being condensed the distillate separates in separator 19 `into an upper aqueous layer and a lower epichlorohydrin layer. The separation is effected a't any convenient temperature of .from about 0v to i100" C., preferably 20 to `80 C., although it is desirable t toefect the `separation `at as low a temperature as practicable. The `water `layer is withdrawn through valve 20 and `contains only about 5 to 10% of epichlorohydrin. Itv

may be collected and subjected to distillation for recovery ofthe epichlorohydrin. The lower epichlorohydrin layerY is substantially pureepichlorohydrin, usually containing less .than about 1.5% water. The epichlorohydrin layer is ordinarily `returned to the reaction mixture through valve 21,"valfve 22 being closed.

` Reaction mixture 17 is withdrawn from reactor 13 by pump25 through valve 26 into second reactor 27. The rate of withdrawal is regulated so that the net liquid contents .of reaction mixture 17 is maintained substantially constant in reactor.13. `This is largely governed by the sum of the rates of introduction of the aqueous caustic,

and the epichlorohydrin and diphenol.

As in reactor 13, the` reaction mixture 248 in reactor 27 is agitated'and heated at boiling temperature. Aqueous caustic ows through valve 29 into reactor Z7 at such a rate as to supply the remainder of the needed equivalent of hydroxide per equivalent of epichlorohydrin that combines with thephenol. As in reactor 13, water is azeotropically distilled from reaction mixture 28 with passage of the vapor to condenser 30 and the condensed distillate to separator 31 where itlikewise separates into anupper water layer anda lower epichlorohydrin. The water layer is `withdrawn through` valve 32 for collection and combining with the water layer-from reactor 13.` The epichlorohydrin layer is, usually `returned to `reactor 27 through valve 33 by having valve 34 closed. If desired, however, the epichlorohydrin layers in one or both sep- 4 epichlorohydrin to vfirst reactor 13. The reaction product is witdhrawn from reactor 27 through valve 35, the rate of withdrawal again being regulated so that the liquid contents of reaction mixture 28 in the reaction zone is maintained substantially constant.

Any number of reactorsl may be connected in series in themanner shown for reactors 13 and 27. However, from a practical standpoint, it is rarely desirable to use more than two, or possibly three reactors in series. The ow of reaction mixture through the several reactors is preferably conducted at a rate such that substantially all of the phenolic hydroxyl groups are etheried in the reaction system, i. e., that the residence time of reaction mixture and volume of the reactors is such that the product withdrawn from the last reactor is substantially free of phenolic hydroxyl groups as may be ascertained by customary chemical analysis. Although it is preferred to operate the process with removal of water from each reaction zone so that the water concentration is main-` tained at a low value, the process is also applicable to operation that does not involve such water removal. The process may thus be applied to a flow reactor having Zones of reaction separated by bailles if desired with introduction of the hydroxide in fractions to the several zones and simply flowing the reactor contents therethrough without water removal from the individual zones. The glycidyl ether of the polyhydric phenol is recovered from the crudereaction product in any suitable manner, The principal constituents in the product are the glycidyl ether, unreacted epichlorohydrin and formed alkali metal chloride salt. It is convenient to rst filter the salt from the product. In order to recover the glycidyl ether from the saltV cake, the cake is washed with epichlorohydrin or a lower alcohol such as isopropyl-alcohol and the washings combined with the ltrate. The liltrate is then distilled to remove epichlorohydrin and salt-washing solvent. Another method for recovery of the glycidyl ether from the crude product involves first subjecting the product to distillation for removal of the epichlorohydrin. 'Ifouthe residuum may then be added an organic liquid in which the glycidyl ether is soluble and the salt substantially insoluble such as benzene, toluene, xylene, methyl isobutyl ketone, or a mixture of an aromatic hydrocarbon land a lower aliphatic ketone, e. g., toluene and methyl ethyl ketone. It is desirable that water be at least substantially immiscible with the organic liquid since after addition of about 25 to 200 or 300% of an equal volume of organic liquid to the epichlorohydrinfree residuum, the salt may be washed from the mixture with water. IfV desired, Vthe salt may be separated by liltration. The organic liquid isinally removedfrom the glycidyl ether product by distillation.

Although `the process of the invention is particularly suitable for continuous production of glycidyl ethers of dihydric'pheno'ls, it 4may bemused for efiicient manufacture of `any`suit-able polyhydric phenol. Typical phenols include those having` phenolic hydroxyl groups attached` to non-adjac`ent `ring carbon atoms such as resorcinol, -hydroquinone, chlorohydroquinones, methyl resorcinol, ,phloroglucinoh 1,5 dihydroxynaphthalene, 4,4'dihydroxydiphenyl, bis(hydroxyphenyl)methane, 1,1- bis(4 hydroxyphenyl)ethane, 1,1 bis(4 hydroxyphenyl)isobutane,V 2,2 bis(4 hydroxyphenyDpropane, which is termed bis-phenol `.herein for convenience, 2,2- bis`(2 hydroxy 4V- Vtert butylphenyl)propane, 2,2-bis- (2 hydroxyphenyl)propane, 2,4 dihydroxydiphenylarators19 and 31 may beA diverted from direct return f by opening valves 22 and 34 with closure of valves 21 and 33. In such case, the'epichlorohydrin layers may be collected, and `if desired, `returned as part lof the feed dimethylmethane, `2,2-bis (2-chloro-4-hydroxyphenyl) propane, 1 2,2 bis(2 hydroxynaphthyl)pentane, 2,2 bis- (2,5 dibromo 4 hydroxyphenyl)butane, 4,4 dihydroxybenzophenone, 1,3 Ybis(4 hydroxyphenyloxy) 2- hydro'xypropane,A 4,4',4"tris(4 hydroxyphenyl)methane, 3`hydrzvxyphenylV salicylate, t 4-salicoylaminophenol, as well as more complex polyhydric phenols such asnovolar,`

' therein.

of and are free of other functional groups which would interfere with formation of the desired glycidyl ethers. It is evident that the process is very useful for production of the valuable -glycidyl ethers of polyhydric phenols.

The invention is illustrated in the following examples, but it is not to 'be construed as limited to details described Example 1 Continuous production of fglycidyl ether of bis-phenol was effected Yin 'an apparatus having two reactors like that illustrated in the drawing, the tirst reactor having a volume of 750 ml. and the second 1500 ml. A solution of bis-phenol in epichlorohydrin containing a mole ratio of epichlorohydrin to bis-phenolA of l/1y was fed at a rate of 2600 grams per hour into'the first reactor. This amounted to an introduction of 1.0 mole of bis-phenol per liter of total reactor space per hour. Aqueous sodium hydroxide ,containing 40% `byweight of the hydroxide was fed into the lirst reactor at a rate of 200 grams per hour. This was about 46.5% of the total hydroxide introduced into the reaction mixture. The mixture in the first reactor was ystirred and boiled at about 108 C. with removalof water by azeotropic ydistillation with epichlorohydrin, n was withdrawn and fedv directly toa second reactor wherein the mixture was stirred land boiled at 108 C. so as to remove water. The remainder of the needed aqueous sodium hydroxide was fed to the second reactor at a rate of 230 grams per hour. Crude reaction product was withdrawn continuously from the second reactor, the

liquid contents in both reactors being maintained substantially constant throughout the run. The crude reaction product was collected and filtered to remove the salt (NaCl). The salt was washed with -anhydrous isopropanol to adhering glycidyl ether and the wash was combined with the filtrate. The filtrate was distilled to separate unreacted epichlorohydrin and the isopropanol, and leave the glycidyl ether as residue.

The glycidyl ether had an average molecule weight of 387 as determined ebullioscopically in ethylene dichloride, and an epoxy value of 0.471 epoxy equivalent per The reaction mixture from Vthe first reactorV 100 grams. Analysis showed this epoxy resin to contain v 69 mole percent of the diglycidyl ether having n=0, and 2O mole percent of the diglycidyl ether having n=1, the value of n referring tothe formula given in the second paragraph of this specification. The remaining 1l mole percent was made up of various miscellaneous byproducts.

- Example 2 By way of comparison, continuous production of glycidyl ether of bis-phenol was effected Vin a single stage reaction system using the same rate of introduction of 1.0 mole of bis-phenol per liter of reactor space per hour. The feed consisted of a solution of bis-phenol in epichlorohydrin containing a mole ratio of epichlorohydrin to bis-phenol of 8/ 1. Experience had shown that no appreciable difference in yield of the desired diglycidyl diether of bis-phenol (n=0) could be attributed to change in the mole ratio from 10/1 to 8/1. The solution of bis-phenol was introduced at a rate of 700 grams per hour into the single reactor along with 40% aqueous sodium hydroxide at a rate of 131 grams per hour. The mixture was stirred and boiled in the reactor at about 107 C. with removal of water by azeotropic '6 distillation with epichlorohydrin. The crude-reaction product was withdrawnvat such a rate that the reactor was maintained substantially full of reaction mixturek as inqExample -1.` The glycidyl ether was isolated as in Example 1.

The glycidyl ether had an average molecular weight of v432 by ebullioscopic measurement in ethylene dichloride and an epoxy value of 0.437 epoxy equivalent per 100 grams. Analysis showed this epoxy resin to contain only 53 mole percent of the diglycidyl ether having n=0, and 36 mole percent of the diglycidyl ether having n=l.

Example 3 The reaction mixture was withdrawn from theirst reactor and flowed continuously to the second reactor from which the reaction product was withdrawn, the rates of ilow being regulated so the contents of the two vrealctofrswere'l substantially constant and full. The 'mixtures 'TinV each reactor were stirred and boiled at about 107 C. with azeotropic distillation of water therefrom with epichlorohydrin.` The glycidyl ether was isolated asin Example 1'.

'.'The glycidyl ether had an average molecular weight of 367;' according to ebullioscopic measurement with ethylene dichloride, and an epoxy value of-0`.491 epoxy equivalent per 100 grams. Analysis showed the glycidyl ether to contain 78 mole percent of the diglycidyl ether having n=0 and 13 mole percent of the diglycidyl ether having n=l.

Example4 Another comparative run was made with the single stage reactor as in Example 3. A solution containing a mole ratio of epichlorohydrin to bis-phenol of 15/1 was introduced into the reactor at a rate of 880 grams per hour along with 48% aqueous sodium hydroxide at a rate of grams per hour. The bis-phenol was introduced at a rate Vof 0.7 mole per liter of reactor space per hour. While stirring and boiling the reaction mixture at a temperature of 102 C., the water was removed azeotropically with epichlorohydrin. The glycidyl ether product was isolated as described above.

The ether had an average molecular weight of 420 by ebullioscopic measurement with ethylene dichloride, and an epoxy value of only 0.405 epoxy equivalent per grams. Analysis showed that the ether contained only 62 mole percent of the diglycidyl ether having n=0 and 26 mole percent of the diglycidyl ether having n=l.

I claim as my invention:

1. In a process for continuous production of polyglycidyl ether of a polyhydric phenol wherein a polyhy- `dric phenol and sufcient epichlorohydrin to amount to at least two molecules thereof per phenolic hydroxyl group are introduced continuously to the rst of a series of reaction zones for reaction with alkali metal hydroxide, reaction mixture is continuously transferred from zone to zone in the series with continuous withdrawal from the last zone, and the reaction mixture in the several zones is agitated and 'boiled with azeotropic distillation of water and epichlorohydrin therefrom so thaty the water concentration in the reaction mixture isV maintained at from about 0.5 to 2% by weight while regulating the rates of introduction of reactants, transfer of reaction mixture and withdrawal of product so the liquid contents in the several zones are maintained substantially conepichlorohydrinl and an alkali metal hydroxide are vreactedin a mixture `,which is agitated and boiled while distilling'water'therefrorn azeotropically with epich1orohydrin `so that the water concentration in the reaction mixture is maintained from about 0.2 to 4% by weight, the improvement of effecting continuous production of the ipolygl'ycidyl `ether bycontinuously introducing the polyhydric` phenol and sufiicient epichlorohydrin to amountltoyat least two molecules thereof per phenolic hydroxyl group, ofthe phenol to the first of a series `of reaction zones, continuously transferring reaction `mixture `from.zone to zone in the series with continuous withdrawal from the last zone, and continuously introducing the hydroxide to the several zones in fractions with `the totaly thereof .amounting to about an equivalent i of `the hydroxide per equivalent` of` the epichlorohydrin that reacts `in the whole ofj the series of zones,k the rates ofiintroduction of reactants, transfer of reaction mixture z' from -zone to zone, and withdrawal of productfrom the last zone rbeing regulated so that the liquid `contents in the several zones are maintained substantially constant.

, -3.,A `process for the Lcontinuousproduction ofkd- 8 rst zone and the total of the'two fractions being about anvequivalent of .the hydroxideper-equivalent of the epichlorohydrin that reacts in the whole of the series of zones,^ and continuously transferring reaction mixture from` 'the firstzone to the second whilecontinuously withdrawing product from `the second, the reaction mixture in thezones being agitated and boiled with azeotropic distillation of water and epichlorohydrin therefrom so that the water concentration in the reaction mixture is Vmaintained at from about 0.5 to 2% by weight, and the rates of introduction of reactants, transfer of reaction mixture-from zone to zone, and withdrawal of product from thelast zone being regulated so that theliquid contents in the two zones are maintained substantially constant. n Y t Y n 4. The process as dened in'clairn wherein the distillate of water and A,epichlorohydrin from each reaction zone is condensed, the condensate is separated into two liquid phases, and the e pichlorohydrin `rich lower layerlis returned to itsv reaction zone in continuous manner.Y i i v5. The process as ,defined in claim 4 wherein the dihydric `phenol is 2,2-,bis(4hydroxyphenyl)propane, the alkali metal hydroxide issodium hydroxide, and the sodium hydroxideis introduced as, anY aqueous solution containing fromabout 15% by weight up to the saturation concentration of the hydroxide.

f References Cited in the Afile of this patent vUmTED STATES PATENTS v stein oct. 25, 193s 2,467,171 Werneret al Apr. 12, 1949 2,642,412 Newey et al. June 16, 1953 2,663,699 Bloem et al. Dec. 22, 1953 

1. IN A PROCESS FOR CONTINUOUS PRODUCTION OF POLYGLYCIDYL ETHER OF A POLYHYDRIC PHENOL WHEREIN A POLYHYDRIC PHENOL AND SUFFICIENT EPICHOLOHYDRIN TO AMOUNT TO AT LEAST TWO MOLECULES THEREOF PER PHENOLIC HYDROXYL GROUP ARE INTRODUCED CONTINOUSLY TO THE FIRST OF A SERIES OF REACTION ZONES FOR REACTION WITH ALKALI METAL HYDROXIDE, REACTION MIXTURE IS CONTINUOUSLY TRANSFERRED FROM ZONE TO ZONE IN THE SERIES WITH CONTINUOUS WITHDRAWAL FROM THE LAST ZONE, AND THE REACTION MIXTURE IN THE SEVERAL ZONES IS AGITATED AND BOILED WITH AZEOTROPIC DISTILLATION OF WATER EPICHLOROHYDRIN THEREFROM SO THAT THE WATER CONCENTRATION IN THE REACTION MIXTURE IS MAINTAINED AT FROM ABOUT 0.5 TO 2% BY WEIGHT WHILE REGULATING THE RATES OF INTRODUCTION OF REACTANTS, TRANSFER OF REACTION MIXTURE AND WITHDRAWAL OF PRODUCT SO THAT LIQUID CONTENTS IN THE SEVERAL ZONES ARE MAINTAINED SUBSTANTIALLY CONSTANT, THE IMPROVEMENT WHICH COMPRISES INTRODUCING THE HYDROXIDE TO THE SEVERAL ZONES IN RACTIONS WITH THE TOTAL THEREOF AMOUNTING TO ABOUT AN EQUIVALENT OF THE HYDROXIDE PER EQUIVALENT OF THE EPICHLOROHYDRIN THAT REACTS IN THE WHOLE OF THE SERIES OF ZONES. 